Laundering aid

ABSTRACT

A laundering aid comprising a water-insoluble, polyurethanepolyalkyleneimine material releasably combined with a detergent composition, said aid providing a means of introducing a detergent composition into a laundry bath and at the same time serving to adsorb dirt and vagrant anionic dyes from the aqueous laundry media, thereby providing an improved laundering process.

United States Patent 1 1 [111 3,816,321 Kleinschmidt June 1 1 1974LAUNDERING AID 3,686,025 8/1972 Mortog 252/91 x 6 [75] Inventor: DavidChares Kleinschmidt, 3,694,364 9/197- Edwar S 252/90 Cincinnati, OhioFOREIGN PATENTS OR APPLICATIONS Assigneel The Procter & Gamble C p y,665,293 Belgium 260/858 Cincinnati, Ohio Primary ExammerHerbert B. GuynnFlled: May 1972 Assistant ExaminerDennis L. Albrecht [2]] Appl No;249,810 Attorney, Agent, or FirmJack D. Schaefi'er; Thomas H. OFlaherty;Richard C. Witte [52] US. Cl 252/134, 8/137, 252/89, A

252/91, 252/117, 252/174, 252/544, 252/547 [57] B,S,TRACT [51 1 Int Cl.oz 1/60, z 1 /72, C] m 17/04 A laundering aid comprising awater-1nsoluble, polyur- [58] Field of Search 252/89 90 91 134 l 17 10lyalky1eneimine material releasably comd 3 bined with a detergentcomposition, said aid providing a means of introducing a detergentcomposition into a [56] References Cited laundry bath and at the sametime serving to adsorb dirt and vagrant anionic dyes from the aqueouslaun- UNITED STATES PATENTS dry media, thereby providing an improvedlaundering 2,813,775 11/1957 Steuber 260/775 C process 3.165566 1/1965Murphy.... 3.283.357 1 H1966 Decker 252/91 9 Claims, No DrawingsLAUNDERING AID BACKGROUND OF THE INVENTION This invention encompasseslaundering aids comprising a chemically modified polyurethane materialin combination with a soap or synthetic organic detergent composition.In its method aspect, the invention comprises the use of the chemicallymodified polyurethane material in aqueous laundry baths to scavenge dirtand anionic dyes released from the fabrics being laundered.

Most laundering compositions contain various synthetic materials capableof suspending dirt released from fabrics during the laundering process.Without such additives much of the dirt released during washing isredeposited on the fabric surface. Even so, washing machinemanufacturers have been constrained to design machines wherein the washwater does not drain through the clothes since even the suspended soilwould then be redeposited on the fabric surface. Another problemencountered during the laundering of fabrics is that of dye transfer.Dye transfer is most evident when deeply colored fabrics are launderedin the same bath with less highly colored, or white, fabrics.Heretofore, there has been no good way to combat the problem of dyetransfer other than mechanically sorting the fabrics to partition saidfabrics into dark and light shades for separate laundering.

U.S. Patent No. 3,424,545, Jan 28, 1969, to R. A. Bauman, discloses aphosphorylated cloth which is added to laundry baths to remove inorganiccations but which does not remove organic anions and dirt as isaccomplished with the present invention. U.S. Pat. No. 3,694,364, Sept.26, 1972, to .l. B. Edwards, relates to the use of cellulosic materialscoated with alkanoylated polyalkyleneimines in laundering baths. Whilethe laundering aids of Edwards are effective, their manufacture requiresa three-step processinvolving formation of the fabric, its surfacemodification and a final surface treatment.

It has now been found that certain water-insoluble polyurethanesubstrates to which are chemically affixed various polyalkyleneiminematerials during the polyurethane polymerization, all as hereinafterdetailed, can be added to aqueous laundering solutions to scavenge ortrap dirt and vagrant anionic dyes from the solution. As an article ofmanufacture, the polyurethane-polyalkyleneimine material also contains adetergent composition which is released into the bath. Thus, the usercan add a predetermined amount of detergent to the bath in conjunctionwith the dye and dirt trapper material. Following the launderingoperation, the dirt and anionic dye trapper material can be removed fromthe aqueous laundry bath, together with the dirt and anionic dyesadsorbed thereon, and discarded.

The polyurethane-polyalkylenimine material employed in the presentinvention is known in the art. For example, U.S. Pat. No. 3,165,566discloses a process for curing polyurethane by passing urethaneprepolymer through a polyamine. The resulting filaments can be woveninto trapper cloths of the type used herein. Foamed polyurethanes of thetype suitable for use herein are disclosed in Belgian Patent No.665,293; U.S. Pat. No. 2,813,775 discloses polyisocyanates containingpolyamides. However, the use of the foregoingpolyalkyleneimine-polyurethane materials in combination with detergentcomponents or as anionic dirt and dye trappers has not been suggestedheretofore.

It is a primary and major object of the present invention tO provide animproved laundering aid capable of performing a fabric cleansingfunction and at the same time adsorbing negatively charged particulatematter (especially dirt) and dissolved organic anionic matter(especially dyes) on its surface. Another object is to provide animproved laundering process. These and other objects are obtained by thepresent invention as will be seen from the following disclosure.

SUMMARY OF THE INVENTION The invention comprises a detergent compositionin releasable combination with a water-insoluble substrate consisting ofpolyurethane in chemical combination with a polyalkyleneimine material.In its process aspect the invention encompasses adding a waterinsolublepolyurethane-polyalkyleneimine substrate to an aqueous washing solutioncontaining a detergent composition to trap dirt and organic anionicmaterials.

DETAILED DESCRIPTION OF THE INVENTION The laundering aids hereincomprise: (I) a waterinsoluble substrate consisting of polyurethanewhich is chemically combined with at least about 0.1 percent, morepreferably from about 1 percent to about 10 percent, by weight ofsubstrate of a polyalkyleneimine material containing the moiety 1wherein y is an integer of from I to 4, z is an integer greater than I,R is selected from the group consisting of hydrogen and alkyl andalkanoyl substituents containing from about I to about 22 carbon atoms,each R is an alkyl group containing from I to about 22 carbon atoms, andX is an anion such as methylsulfate, halogen, sulfate, hydroxide and thelike; and (2) a water-soluble detergent composition in releasablecombination with said substrate. When alkylated or alkanoylatedpolyalkyleneimines are used herein, from about 5 percent to about 100percent, more preferably 10 percent to 50 percent, of the nitrogen atomsin the polyalkyleneimine are substituted with alkyl or alkanoyl groupscontaining 1 to 22 carbon atoms. For the purposes of this invention,polyalkyleneimines, including alkylated and alkanoylatedpolyalkyleneimines, of any degree of polymerization, especially those inthe I range of 2 to 50,000, especially 20 to 10,000, monomer units permolecule, are preferred.

Since the polyurethane-polyalkyleneimine substrate materials are usedherein to scavenge, or trap, dirt and anionic dyes released during alaundering process, they are referred to herein as trapper materials ortrappers". While any of the materials prepared in the manner describedin U.S. Pat. Nos. 3,165,566 and 2,813,775 and in Belgian Patent 665,293,incorporated herein by reference, are suitable for use herein as thetrapper material, polyurethane-polyethylene-imine materials arepreferred. Especially preferred for use in the present invention aretrappers comprising waterinsoluble, foamed polyurethane in chemicalcombination with from about 0.5 percent to about 10 percent by weight ofpolyethyleneimine.

The foregoing patents relating to amine-containing polyurethanesdisclose a variety of water-insoluble polyurethane substrates preparedin the presence of various polyalkyleneimines; alkylated andalkanoylated polyalkyleneimines can be employed in the same manner toprovide polyurethanes chemically combined with alkylated andalkanoylated polyalkyleneimines. The resulting materials have thepolyalkyleneimines (or alkylated or alkanoylated polyalkyleneimines)chemically affixed to the polyurethane, presumably by covalent bonding(urea linkages) with the monomer units of the polymer. Any excess,uncombined, polyalkyleneimines can be removed by a water wash. Thechemically bound polyalkyleneimine materials in such compositions arenot removed by contact with water. Any of these water-insolublepolyurethanepolyalkyleneimine trapper materials can be employed hereinin combination with detergents and soaps to provide laundering aids.

The trapper materials herein are prepared by forming polyurethane (froman isocyanate and a polyol) in the presence of a polyalkyleneimine. Thepolyalkyleneimine compounds used to prepare the water-insolublepolyalkyleneiminc-polyurethane materials herein comprise apolyalkyleneimine backbone having pendant hydrogen, or alkyl or alkanoylgroups on the nitrogen atoms. These polymers are difiicult to describein other than a qualitative manner. For example, the preferredpolyalkyleneimine used herein is polyethyleneimine. It is believedthat.the structural formula of polyethyleneimine is:

N- cmcmi r wherein 2 represents a whole number greater than 1, usuallyabout 2 to l00,000. The degree of polymerization, 1, is not critical forthe purposes of this invention. Branched chains occur along thepolymeric backbone and the relative proportions of primary, secondaryand tertiary amino groups present in the polymer will vary, depending onthe manner of preparation. The distribution of amino groups in a typicalpolyethyleneimine is approximately as follows:

The polyethyleneimine can only be characterized in terms of molecularweight. Such polymers can be prepared, for example, by polymerizingethyleneimine in the presence of a catalyst such as carbon dioxide,sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid,acetic acid, etc. Specific methods are described in U.S. Pat. Nos.2,182,306; 3,033,746; 2,208,095; 2,806,839; and 2,552,696, incorporatedherein by reference.

Alkylated and alkanoylated polyethyleneimines are obtained by heatingalkyl halides, organic acids or acid halides with the polyethyleneiminein the manner described in U.S. Pat. Nos. 2,296,226; 2,272,489; and2,l85,480, incorporated herein by reference. The otherpolyalkyleneimines useful herein are prepared in like fashion. Variousratios of alkylating or alkanoylating agent to polyethyleneimine can beemployed so that varying percentages of the nitrogen atoms are therebysubstituted. The percentage of nitrogen substitution can be determined,for example, by examination of the proton resonance or the infraredspectrum of the polymer. The alkylated polyalkyleneimine polyurethanescan be further substituted to yield polyalkyleneimines having thenitrogen substituents quaternarized with alkyl groups R. The resultingalkylated and alkanoylated polyethyleneimines, which have molecularweights in the range of about 1,000 to about I million. are usefulherein.

The trapper substrate prepared in the foregoing manner is preferablyused in releasable combination with a detergent composition, and, in apreferred embodiment, is in bag conformation releasably containing saiddetergent composition. The container is added to the laundry water andthe laundering process is carried out in standard fashion. The trapperbag releases the detergent composition and remains to scavenge dirt andanionic dyes. Alternatively, a trapper in sponge form is impregnated orcoated with a detergent composition which is released on contact withwater. The released trapper sponge then performs its anionic dye anddirt adsorbing function. Still another article comprises a detergentformulation in tablet form having a trapper substrate incorporated inthe interior which is released when the tablet dissolves in water.Exemplary detergent and presoak compositions suitable for use with thetrapper material in the practice of this invention are those typicalcommercial products comprising a mixture of about 10 percent to about100 percent by weight of a water-soluble organic detergent compound;preferred compositions contain from about 10 percent to about percent byweight of a water-soluble detergency builder and from about l0 percentto about 90 percent by weight of the aforesaid organic detergentcompounds. Minor amounts of common laundry additive ingredients, ashereinafter detailed, can also be present. lncluded in this definitionof detergent compositions are built and unbuilt soap compositions anddetergent compositions containing enzymes. The trapper material iscompatible with all manner of those compositions and successfullyaccomplishes its dirt and organic anionic dye trapping function in theirpresence. Surprisingly, although many of the most useful organicdetergent compounds commonly employed in modern laundry detergentcompositions are organic anionic materials, the trapper material doesnot interfere with their cleaning properties.

Non-limiting examples of typical water-soluble synthetic organicdetergents, enzymes, soaps and builders, along with typical compositionscontaining them, which are suitably employed in conjunction with thetrapper material to provide a laundering aid are more fully describedbelow. Usually, from about 2 oz. to about 6 oz. of such compositions areused in conjunction with the trapper, but this is not critical in thatany amount of such compositions sufficient to provide good fabriccleansing can be so employed.

Organic Detergents The organic detergent compounds which can be utilizedwith the trapper material in the laundering aids encompassed by thisinvention include the following:

A. Anionic Soap and Non-Soap Synthetic Detergents This class ofdetergents includes ordinary alkali metal soaps such as the sodium,potassium, ammonium and alkanol-ammonium salts of higher fatty acidscontaining from about 8 to about 24 carbon atoms and preferably fromabout to about 20 carbon atoms. Suitable fatty acids can be obtainedfrom natural sources such as, for instance, plant or animal esters(e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil,tallow, whale and fish oils, grease, lard, and mixtures thereof). Thefatty acids also can be synthetically prepared (e.g., by the oxidationof petroleum, or by hydrogenation of carbon monoxide by theFischer-Tropsch process). Resin acids are suitable such as rosin andthose resin acids in tall oil. Naphthenic acids are also suitable.Sodium and potassium soaps can be made by direct saponification of thefats and oils or by the neutralization of the free fatty acids which areprepared in a separate manufacturing process. Particularly useful arethe sodium and potassium salts of the mixtures of fatty acids derivedfrom coconut oil and tallow, i.e., sodium or potassium tallow andcoconut soap.

This class of detergents also includes water-soluble salts, particularlythe alkali metal salts, of organic sulfuric reaction products having intheir molecular structure an alkyl radical containing from about 8 toabout 22 carbon atoms and a sulfonic acid or sulfuric acid esterradical. (Included in the term alkyl is the alkyl portion of higher acylradicals.) Examples of this group of synthetic detergents which form apart of the preferred built detergent compositions of the presentinvention are the sodium or potassium alkyl sulfates, especially thoseobtained by sulfating the higher alcohols (C C carbon atoms produced byreducing the glycerides of tallow or coconut oil; sodium or potassiumalkyl benzene sulfonates, in which the alkyl group contains from about 9to about carbon atoms in straight chain or branched chain configuration,e.g., those of the type described in U.S. Pat. Nos. 2,220,099 and2,477,383 (especially valuable are linear straight chain alkyl benzenesulfonates in which the average of the alkyl groups is about 12 carbonatoms and commonly abbreviated as C LAS); sodium alkyl glyceryl ethersulfonates,especially those ethers of higher alcohols derived fromtallow and coconut oil; sodiumcoconut oil fatty acid monoglyceride'sulfonates and sulfates; sodium or potassium salts of sulfuric acidesters of the reaction product of one mole of a higher fatty alcohol(e.g., tallow or coconut oil alcohols) and about I to 6 moles ofethylene oxide; sodium or potassium salts of alkyl phenol ethylene oxideether sulfate with about 1 to about 10 units of ethylene oxide permolecule and in which the alkyl radicals contain about 8 to about 12carbon atoms.

Anionic phosphate surfactants are also useful in the present invention.These are surface active materials having substantial detergentcapability in which the anionic solubilizing group connectinghydrophobic moieties is an oxy acid of phosphorus. The more commonsolubilizing groups, of course, are SO l-l, SO H, and --CO H. Alkylphosphate esters such as (RO) PO H and ROPO l-l in which R represents analkyl chain containing from about 8 to about carbon atoms are useful.

These esters can be modified by including in the mol ecule from one toabout 40 alkylene oxide units, e.g., ethylene oxide units. Formulae forthese modified phosphate anionic detergents are in which R represents analkyl group containing from about 8 to 20 carbon atoms, or analkylphenyl group in which the alkyl group contains from about 8 to 20carbon atoms, and M represents a water-soluble cation such as hydrogen,sodium, potassium, ammonium or substituted ammonium; and in which n isan integer from 1 to about 40.

Another class of suitable anionic organic detergents particularly usefulin this invention includes salts of 2-acyloxyalkane-l-sulfonic acids.These salts have the formula ii (1)0112 R1C H-CHzS03M where R is alkylof about 9 to about 23 carbon atoms (forming with the two carbon atomsan alkane group); R is alkyl of l to about 8 carbon atoms; and M is awater-soluble cation.

The water-soluble cation, M, in the hereinbefore described structuralformula can be, for example, an alkali metal cation (e.g., sodium,potassium, lithium), ammonium or substituted-ammonium cation. Specificexamples of substituted ammonium cations include methyl-, dimethyl-, andtrimethylammonium cations and quaternary ammonium cations such astetramethyl-ammonium and dimethyl piperidinium cations and those derivedfrom alkylamines such as ethylamine, diethylamine, triethylamine,mixtures thereof, and the like.

Specific examples of B-acyloxy-alkane-l-sulfonates, or alternatively2-acyloxy-alkane-l-sulfonates, useful herein to provide superiorcleaning levels under substantially neutral washing conditions includethe sodium salt of 2-acetoxy-tridecane-l-sulfonic acid; the potassiumsalt of 2-propionyloxy-tetradecane-lsulfonic acid; the lithium salt of2-butanoyloxytetradecane-l-sulfonic acid; the sodium salt of 2-pentanoyloxy-pentadecane-l-sulfonic acid; the sodium salt ofZ-acetoxy-hexadecane-l-sulfonic acid; the potassium salt of2-octanoyloxy-tetradecane-l-sulfonic acid; the sodium salt of2-acetoxy-heptadecane-lsulfonic acid; the lithium salt of2-acetoxy-octadecanel-sulfonic acid; the potassium salt of2-acetoxynonadecane-l-sulfonic acid; the sodium salt of2-acetoxy-uncosane-l-sulfonic acid; the sodium salt of2-propionyloxy-docosane-l-sulfonic acid; the isomers thereof.

Preferred B-acyloxy-alkane-l-sulfonate salts herein are the alkali metalsalts of B-acetoxy-alkane-l-sulfonic acids corresponding to the aboveformula wherein R is alkyl of about 12 to about 16 carbon atoms, thesesalts being preferred from the standpoints of their excellent cleaningproperties and ready availability.

Typical examples of the above-described B-acetoxy alkanesulfonates aredescribed in the literature: Belgium Patent 650,323 discloses thepreparation of certain 2-acyloxy alkanesulfonic acids. Similarly, U.S.Pat. No. 2,094,451 and 2,086,215 disclose certain salts of B-acetoxyalkanesulfonic acids. These patents are hereby incorporated byreference.

Another preferred class of anionic detergent compounds herein, both byvirtue of superior cleaning properties and low sensitivity to waterhardness (Ca-1+ and Mg-H' ions) are the alkylated a-sulfocarboxylates,containing about 10 to about 23 carbon atoms, and having the formulawhere R, is a straight chain alkyl group having from 6 to 20 carbonatoms, R; is a lower alkyl group having from 1 (preferred) to 3 carbonatoms, and M is a watersoluble cation as hereinbefore described.

Specific examples of B-alkyloxy alkane sulfonates, or alternatively2-a1ky1oxy-alkane-l-sulfonates, having low hardness (calcium ion)sensitivity useful herein to provide superior cleaning levels underhousehold washing conditions include:

potassium-,B-methoxydecanesulfonate,

sodium 2-methoxytridecanesulfonate,

potassium 2-ethoxytetradecylsulfonate,

sodium 2-isopropoxyhexadecylsulfonate,

lithium Z-t-butoxytetradecylsulfonate,

sodium B-methoxyoctadecylsulfonate, and

ammonium B-n-propoxydodecylsulfonate.

Other synthetic anionic detergents useful herein are alkyl ethersulfates. These materials have the formula RO(C H O),SO M wherein R isalkyl or alkenyl of about to about 20 carbon atoms, x is 1 to 30, and Mis a water-soluble cation as defined hereinbefore. The alkyl ethersulfates useful in the present invention are condensation products ofethylene oxide and monohydric alcohols having about 10 to about 20carbon atoms. Preferably, R has 14 to 18 carbon atoms.

The alcohols can be derived from fats, e.g., coconut oil or tallow, orcan be synthetic. Lauryl alcohol and straight chain alcohols derivedfrom tallow are preferred herein. Such alcohols are reacted with 1 to30, and especially 6, molar proportions of ethylene oxide and theresulting mixture of molecular species, having, for example, an averageof 6 moles of ethylene oxide per mole of alcohol, is sulfated andneutralized.

Specific examples of alkyl ether sulfates of the present invention aresodium coconut alkyl ethylene glycol ether sulfate; lithium tallow alkyltriethylene glycol ether sulfate; and sodium tallow alkylhexaoxyethylene sulfate.

Preferred herein for reasons of excellent cleaning properties and readyavailability are the alkali metal coconutand tallow-alkyl oxyethyleneether sulfates having an average of about 1 to about 10 oxyethylenemoieties. The alkyl ether sulfates of the present invention are knowncompounds and are described .in U.S. Pat. No. 3,332,876, incorporatedherein by reference.

Additional examples of anionic non-soap synthetic detergents which comewithin the terms of the present invention are the reaction product offatty acids esterified with isethionic acid and neutralized with sodiumhydroxide where, for example, the fatty acids are derived from coconutoil; sodium or potassium salts of fatty acid amides of methyl tauride inwhich the fatty acids, for example, are derived from coconut oil. Otheranionic synthetic detergents of this variety are set forth in U.S. Pat.Nos. 2,486,921; 2,486,922; and 2,396,278.

Additional examples of anionic, non-soap, synthetic detergents, whichcome within the terms of the present invention, are the compounds whichcontain two anionic functional groups. These are referred to asdianionic detergents. Suitable di-anionic detergents are thedisulfonates, disulfates, or mixtures thereof which may be representedby the following formulae:

3)2 2 4)z z, 3)( 4) 2 where R is an acyclic aliphatic hydrocarbyl grouphaving 15 to 20 carbon atoms and M is a water-solubilizing cation, forexample, the C to C disodium 1,2- alkyldisulfates, C to Cdipotassium-l,2-alkyldisulfonates or disulfates, disodium 1,9-hexadecy1disulfates, C to C disodium-1 ,2-alkyldisulfonates, disodium 1 ,9-stearyldisulfates and 6,10-octadecyldisulfates.

The aliphatic portion of the disulfates or disulfonates is generallysubstantially linear, thereby imparting desirable biodegradableproperties to the detergent compound.

' The water-solubilizing cations include the customary cations known inthe detergent art, i.e., the alkali metals, and the ammonium cations, aswell as other metals in group 11A, 11B, 111A, IVA and [VB of thePeriodic Table except for boron. The preferred watersolubilizing cationsare sodium or potassium. These dianionic detergents are'more fullydescribed in British Letters Patent 1,151,392.

Still other anionic synthetic detergents include the class designated assuccinamates. This class includes such surface active agents as disodiumN-octadecylsulfo-succinamate; tetrasodium N-( 1,2-dicarboxyethyl)-N-octadecylsulfo-succinamate; diamyl ester of sodium sulfosuccinic acid;dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of sodiumsulfosuccinic acid.

Other suitable anionic detergents utilizable herein are olefinsulfonates having about 12 to about 24 carbon atoms. The term olefinsulfonates is used herein to mean compounds which can be produced by thesulfonate of a-olefms by means of uncomplexed sulfur trioxide, followedby neutralization of the acid reaction mixture in conditions such thatany sultones which have been formed in the reaction are hydrolyzed togive the corresponding hydroxy-alkane-sulfonates. The sulfur trioxidecan be liquid or gaseous, and is usually, but not necessarily, dilutedby inert diluents, for example by liquid S chlorinated hydrocarbons,etc., when used in the liquid form, or by air, nitrogen, gaseous S0etc., when used in the gaseous form.

The a-olefins from which the olefin sulfonates are derived aremono-olefins having 12 to 24 carbon atoms, preferably 14 to 16 carbonatoms. Preferably, they are straight chain olefins. Examples of suitablel-olefins include l-dodecene; l-tetradecene; l-hexadecene; 1-octadecene; l-eicosene and l-tetracosene.

in addition to the true alkene sulfonates and a proportion ofhydroxy-alkanesulfonates, the olefin sulfonates can contain minoramounts of other materials, such as alkene disulfonates depending uponthe reaction conditions, proportion of reactants, the nature of thestarting olefins and impurities in the olefin stock and side reactionsduring the sulfonate process.

A specific anionic detergent which has also been found excellent for usein the present invention is described more fully in the US. Pat. No.3,332,880, incorporated herein by reference.

B. Nonionic Synthetic Detergents Nonionic synthetic detergents may bebroadly defined as compounds produced by the condensation of alkyleneoxide groups (hydrophilic in nature) with an organic hydrophobiccompound, which may be aliphatic or alkyl aromatic in nature. The lengthof the hydrophilic or polyoxyalkylene radical which is condensed withany particular hydrophobic group can be readily adjusted to yield awater-soluble compound having the desired degree of balance betweenhydrophilic and hydrophobic elements.

For example, a well known class of nonionic synthetic detergents is madeavailable on the market under the trade name of Pluronic. Thesecompounds are formed by condensing ethylene oxide with a hydrophobicbase formed by the condensation of propylene oxide with propyleneglycol. The hydrophobic portion of the molecule which, of course,exhibits water insolubility, has a molecular weight of from about 1500to 1800. The addition of polyoxyethylene radicals to this hydrophobicportion tends to increase the water solubility of the molecule as awhole and the liquid character of the product is retained up to thepoint where polyoxyethylene content is about 50 percent of the totalweight of the condensation product.

Other suitable nonionic synthetic detergents include:

1. The polyethylene oxide condensates of alkyl phenols, e.g., thecondensation products of alkyl phenols having an alkyl group containingfrom about 6 to 12 carbon atoms in either a straight chain or branchedchain configuration, with ethylene oxide, the said ethylene oxide beingpresent in amounts equal to to 25 moles of ethylene oxide per mole ofalkyl phenol. The

alkyl substituent in such compounds may be derived from polymerizedpropylene, diisobutylene, octene, or nonene, for example.

2. Compounds derived from the condensation of ethylene oxide with theproduct resulting from the reaction of propylene oxide and ethylenediamine. For example, compounds containing from about 40 percent toabout percent polyoxyethylene by weight and having a molecular weight offrom about 5,000 to about 11,000 resulting from the reaction of ethyleneoxide groups with a hydrophobic base constituted of the reaction productof ethylene diamine and excess propylene oxide, said base having amolecular weight of the order of 2,500 and 3,000, are satisfactory.

3. The condensafion product of aliphatic alcohols having from 8 to 22carbon atoms, in either straight chain or branched chain configurationwith ethylene oxide, e.g., a coconut alcohol-ethylene oxide condensatehaving from 5 to 30 moles of ethylene oxide per mole of coconut alcohol,the coconut alcohol fraction having from 10 to 14 carbon atoms.

4. Nonionic detergents include nonyl phenol condensed with about 10 toabout 30 moles of ehtylene oxide per mole of phenol; the condensationproducts of ethylene alcohol with an average of either about 5.5 orabout 15 moles of ethylene oxide per mole of alcohol, and, thecondensation product of about 15 moles of ethylene oxide with one moleof tridecanol.

Other examples include dodecylphenol condensed with 12 moles of ethyleneoxide per mole of phenol; dinonylphenol condensed with 15 moles ofethylene oxide per mole of phenol; dodecyl mercaptan condensed with 10moles of ethylene oxide per mole of mercaptan;bis-(N-Z-hydroxyethyl)lauramide; nonyl phenol condensed with 20 moles ofethylene oxide per mole of nonyl phenol; myristyl alcohol condensed with10 moles of ethylene oxide per mole of myristyl alcohol; lauramidecondensed with 15 moles of ethylene oxide per mole of lauramide; anddi-isooctylphenol condensed with 15 moles of ethylene oxide.

5. A detergent having the formula R R R N O (amine oxide detergent)wherein R is an alkyl group containing from about 10 to about 28 carbonatoms,-

from 0 to about 2 hydroxy groups and from 0 to about 5 ether linkages,there being at least one moiety of R which is an alkyl group containingfrom about 10 to about 18 carbon atoms and 0 ether linkages, and each Rand R are selected from the group consisting of alkyl radicals andhydroxyalkyl radicals containing from 1 to about 3 carbon atoms.

Specific examples of amine oxide detergents include:dimethyldodecylamine oxide, dimethyltetradecylamine oxide,ethylmethyltetradecylamine oxide, cetyldimethylamine oxide,dimethylstearylamine oxide, cetylethylpropylamine oxide,diethyldodecylamine oxide, diethyltetradecylamine oxide,dipropyldodecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, bis-(Z-hydroxyethyl )-34iodecoxyl -hydroxypropylamine oxide,(2-hydroxypropyl )methyltetradecylamine oxide, dimethyloleyamine oxide,dimethyl-(2- hydroxydodecyl)amine oxide, and the corresponding decyl,hexadecyl and octadecyl homologs of the above compounds.

6. A detergent having the formula RR R P O (phosphine oxide detergent)wherein R is an alkyl group containing from about 10 to about 28 carbonatoms, from 0 to about 2 hydroxy groups and from 0 tohydroxymethyl)dodecylphosphine oxide, bis-(2-hydroxyethyl)dodecylphosphine oxide, (2-hydroxypropyl)methyltetradecylphosphine oxide,

dimethyloleylphosphine oxide, and dimethyl-(2- hydroxydodecyl)phosphineoxide and the corresponding decyl, hexadecyl, and octadecyl homologs ofthe above compounds.

7. A detergent having the formula rui-m (sulfoxide detergent) wherein Ris an alkyl radical containing from about 10 to about 28 carbon atoms,from O to about 5 ether linkages and from O to about 2 hydroxylsubstituents at least one moiety of R being an alkyl radical containing0 ether linkages and containing from about to about 18 carbon atoms, andwherein R is an alkyl radical containing from 1 to 3 carbon atoms andfrom one to two hydroxyl groups: e.g., octadecyl methyl sulfoxide,dodecyl methyl sulfoxide, tetradecyl methyl sulfoxide, 3-hydroxytridecylmethyl sulfoxide, 3-methoxytridecyl methyl sulfoxide,3-hydroxy-4-dodecoxybutyl methyl sulfoxide, octadecyl Z-hydroxyethylsulfoxide, and dodecylethyl sulfoxide.

C. Ampholytic Synthetic Detergents falling within this definition aresodium 3- (dodecylamino)propionate, sodium 3- (dodecylamino)propane-l-sulfonate, sodium 2- (dodecylamino)ethyl sulfate, sodium 2-(dimethylamino)octadecanoate, disodium 3-(N-carboxymethyldodecylamin0)propanel -sulfonate, disodiumoctadecyl-iminodiazetate, sodium l-carboxymethyl-2-undecylimidazole, andsodium N,N-bis(2- hyd roxyethyl )-2-sulfato-3-dodecoxypropylamine.

D. Zwitterionic Synthetic Detergents Zwitterionic synthetic detergentscan be broadly described as derivatives of aliphatic quaternary ammoniumand phosphonium or tertiary sulfonium compounds, in which the cationicatom may be part of a heterocyclic ring, and in which the aliphaticradical may be straight chain or branched, and wherein one of thealiphatic substituents contains from about 3 to 18 carbon atoms, and atleast one aliphatic substituent contains an anionic water-solubilizinggroup, e.g., carboxy, sulfonate, sulfato, phosphato, or phosphono.Examples of compounds falling within this definition are3-(N,N-dimethyl-N-hexadecylammonio)-2- hydroxypropanel -sulfonate, 3-( N,Ndimethyl-N- hexadecylammonio )propanel -sulfonate, 2-( N,N-dimethyl-N-dodecylammonio)acetate, 3-(N,N- dimethylN-dodecylammonio)-propionate, 2-(N,N-

dimethyl-N-octadecylammonio)ethyl sulfate, 2-(trimethylarnmonio)ethyldodecylphosphonate, ethyl 3-(N,N-dimethyl-N-dodecylammonio)propylphosphonate,3-(P,P-dimethyl-P-dodecylphosphonio)propanel sulfonate,2-(S-methyl-S-tert-hexadecylsulfonio)ethane-l-sulfonate, 3-(S-methyl-S-dodecylsulfonio)propionate, sodium 2-(N,N-dimethyl-N-dodecylammonio)ethyl phosphonate, 4-(S-methyl-Stetra-decylsulfonio)butyrate, l-( 2-hydroxyethyl )-2-undecylimidazoliuml -acetate, 2-(trimethylammonio)octadecanoate, and3-N,N-bis-(2-hydroxyethyl-N- octadecylammonio)-2-hydroxypropanel-sulfonate. Some of these detergents are described in the following US.Pat. Nos. 2,129,264; 2,178,353; 2,774,786; 2,813,898; and 2,828,332. Theammoniopropane sulfonates containing about 8 to about 21 carbon atomsare one class of detergent compounds preferred herein by virtue of theirrelatively low calcium ion (hardness) sensitivity.

These soap and non-soap anionic, nonionic, am-

pholytic and Zwitterionic detergent compounds, either 7 singly or invarious well-known combinations, can be used herein. The above examplesare merely illustrations of the numerous detergents suitable for useherein and it is to be understood that other organic soaps and detergentcompounds can also be used in conjunction with trapper materials toprovide laundering aids.

Builder Salts Many of the common detergent compositions containwater-soluble builder salts, either of the organic or inorganic type;these are wholly compatible with the trapper materials and can be usedin conjunction with organic detergent compounds and trapper materials toprovide laundering aids.

Non-limiting examples of suitable water-soluble, inorganic alkalinedetergency builder salts are the alkali metal carbonates, borates,phosphates, polyphosphates, bicarbonates, silicates and sulfates.Specific examples of such salts are sodium and potassium tetraborates,perborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates,orthophosphates and hexametaphosphates.

Examples of suitable organic alkaline detergency builder salts are: (l)water-soluble aminopolyacetates, e.g., sodium and potassiumethylenediaminetetraacetates, nitrilotriacetates and N-(2-hydroxyethyl)-nitrilodiacetates', (2) water-soluble salts of phytic acid, e.g., sodiumand potassium phytates see US. Pat. No. 2,739,942; (3) water-solublepolyphosphonates, including, specifically, sodium, potassium and lithiumsalts of methylene diphosphonic acid; sodium, potassium and lithiumsalts of ethylene diphosphonic acid; and sodium potassium and lithiumsalts of ethane-1,1,2-triphosphonic acid. Other examples include thesealkali metal salts of ethane-Z-carboxy-l ,ldiphosphonic acid,hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane- 1hydroxyl ,l ,2-

3 ,8 16,321 13 14 triphosphonic acid, ethane-Z-hydroxyl l ,2- Itriphosphonic acid, propanel ,1 ,3,3-tetraphosphonic acid,propane-l,l,2,3-tetraphosphonic acid, and prop- Detergent Composition Cane-l,2,2,3-tetraphosphonic acid, and water-soluble Weight salts ofpolycarboxylate polymers and copolymers such 5 Percent as thosedescribed in U.S. Pat. No. 3,308,067. 175 sodium neardodecylbenzenesulfonm The polycarboxylate materials described in US.Pat. 50 sodium citrate No. 2,264,103, are also suitably employed herein.For 504mm Sulfa? 0.5 sod bo th example, aconitic acid, mellitic acid andthe pentaand 7 :fi ykeuulose tetra-carboxylic acids prepared by themalonic acid 10 010 additive? p synthesis can be employed herein asbuilders. The mmswre water-soluble alkali metal salts of these materialsare Including perfumes and optical brighteners. also suitable.

Mixtures of organic and/or inorganic builders can be used and aregenerally desirable. One such mixture of builders is disclosed inCanadian Patent 755,038, e.g., Detergent Composition D ternary mixturesof sodium tripolyphosphate, trisodium weigh, nitrilotriacetate andtrisodium ethane-l-hydroxy-l,l- Percent diphosphonate. The abovedescribed builders can also 5 dimelhyldodecylphosphine oxide be utilizedsingly in this invention. 10 condensation Pmductof 11 moles f Preferredbuilders herein include: the sodium and pogfiy i z with 1 mole ofcoconut O tassium salts of the tripolyphosphates, nitr lotriac- 10melhylenediphosphonm etates, mellitates (benzenehexacarboxylates),silicates, 8 5 2m pg g l so ium car oxymet yce uose citrates,carbonates, oxydisuccinates, phloroglucinol- 10 Sodium memmctrisulfonates, and (ethylenedioxy)diacetates. bal. moisture Variouspolyelectrolytes such as carboxymethylcellulose,carboxymethylhydroxyethylcellulose, and the like, are commonly added todetergent formulations to provide a soil antiredeposition effect. Anysuch materials are suitable for use in the laundering aids of DemgcmComposition E this invention. yvei m Optical bleaches, such as thestilbenes, furans, thiophenes and the like, are all useful with thelaundering 7 sodium tallowalkyl sulfate aids and can be incorporatedtherein. 7 gi 39 ligdeclyllbtenlenesulfonate SO um The following areexamples of typical detergent and Sodium 555 15,? a e presoakcompositions suitable for use in combination :9 sodium suig ehl H h r Jpotassium ic orocyanurate eac with the trapper materials employed in thepresent in- 005 perfume vention to provide laundering aids. Thecompositions bal. moisture listed are for the purposes of illustrationand are not intended to be limiting of the types of formulations used 40with the trapper materials to provide the laundering aids of thisinvention.

Detergent Composition F (Liquid) Weight Percent Detergent Composition AWeight 6 sodium-3-dodecylaminopropionate Percent 6 sodium lineardodecylbenzenesulfonate 20 potassium pyrophosphate 7.8 sodium lineardodecylbenzenesulfonate 8 P na 9.5 sodium tallowalkyl sulfate SOdlumslllcale 49 4 Sodium mpolyphosphme 50 0.3carboxymethylhydroxyethylcellulose 5 9 Sodium Smcme 0.05 addmves(optional) 13 10 50 bal. water 0.2 sodium carhoxymcthylcellulose 2,2nqninnic suds controlling agents lncluding perfumes and opticalbrighteners.

bal. moisture l m A "M b 1" W Detergent Composition G (Liquid) WeightPercent -t' B weigh Detergent compo 6 sodium lineardodecylbenzenesulfonate Percent 4 dimethyldodecylamine oxide 10trisodium ethanel -hydroxy-l l -diphosphonate l0 tripotassiumnitrilotriacetate 9(5) sog um soap lot 20.80 coconut.tallow fatty acidsI 8 7 Potassium toluenesulfonam 3 e h hm 3.8 sodium silicate (ratio SiO:Na O of 2:1) 1 5 59 "LT R 05p c V 5 V potassium dichlorocyanurate(bleach) Z on l 0.3 sodium carboxymethylcellulose 2 1: 5: (op 0.203-morpliolino-2,5-diphenylfuran (optical brightener) 0.10 perfumeIncluding perfumes and optical brighteners.

Detergent Composition H Detergent Composition L (For Cool Water Use)Weight Weight Percent Percent 40 sodium salt of SO;,-sulfonatedtetradecene H5) zzmaz ggg g $8 ii'i'sii'iiiii'iillfi il '2-"i?o; .e 40sodium 10 Sodium carbon Y P [0 sodium silicate (N a,O:SiO 125 ha!moisture 0.3 sod um oxydlsuccinate 10 sodium (ethylenedroxfidtacetate l0 bal. moisture In the above compositions (with the exception ofDetergent composition l Compositions E and G since these containenzymeweigm destroying bleaches) a minor amount, i.e., from aboutPercent 0.001 percent to about 2 percent, by weight, of an enzyme suchas an amylase, a protease or a lipase, can be 7.5tetradecyl-B-methoxyfitlfonatc added to provide the cleansing advantagesof said en- 2.2 o i l l'atty acid suds depressant zymes' The enzyme usedIn a given composlnon de- 40 sodium tripolyphosphate pend to some extenton the pH, but this selection can 20 trisodiufli I1ilril0 ri I be madeby reference to available pH-activity tables for l0 sod um s licate (2:1ratio Sio zNa o) enzymes. 13 SOdILlm citrate 2g 3:22a The temperature ofthe aqueous medium employed in any of the various stages of launderingprocesses employing the laundering aids of this invention is notcritical in that said aids function well at temperatures from about 32Fto about 212F, preferably from about 75F to about 160F. It is wellestablished that certain laundry detergents and additives are suitablefor use at the weigh Cmpomm lower temperatures within this range whileothers per- Percent form more effectively at higher temperatures. It isfurther recognized that certain whitening agents such as 10 Sodium neardodecylbenzenesuifonm 35 perborate are suitable for use only at thehigher tem- 10 condensation Product of 1 mole 0f nonyl peratures withinthis range. Therefore, the practitioner l0 g 'f f ggggfi gz jf of thisinvention can select a commercial detergent, 30 trisodiumethane-l-hydroxyd,l-diphosphonate bleach, whitener or presoakcomposition which funcg z gg z ii gf z b tions at any desiredtemperature, combine it with the [0 fgisoziium phosphate 2 2 40 trappermaterial and thereby provide a laundering aid 0.5 sodiumcarboxymethylcellulose designed to meet the needs of various launderingsitua- 0. l 3-phenyl-2,S-diphenylthiophene tions.

(optical brightener) -P- The laundering aids of this invention can beprepared baL ggfljfj' bnghtener) using a variety of trapper materialsprepared in the manner of the art and a variety of detergentcompositions much like those available commercially. The examples hereinare intended to illustrate the present invention but are not intended tobe limiting thereof. The terms, 100 percent SPEI, percent SPEI, etc., 5Orelate to the percent of the nitrogen atoms in polyethylweigm K (Fm use)eneimine which are alltylated or alkanoylated. Similar percentterminology IS used with the other alkylated and al- 2 k y a mlyylensimi ss smnt ysdths V 5 sodium {allowalkyl Sulfate The polyurethanesused in the instant invention are the well-known polymeric substancesproduced by the 5 sodium salt of sorsulfonaied -tri n condensation of apolyisocyanate and a polyhydroxylg8 containing material such as apolyol. Though contain- 10 sodium silicate sio,:Nii o L621) ing manyfree urethane or free isocyanate groups, the 10 s i p g g g g giglcenulose molecule may have a number of other constituents. A 31? ifi'lifiifieih i'l'ifimsidi hln iiuiin P y e foam y be a sq idi "a p nperfume foam prepared by reacting a polyether, such as polymoislurcpropylene glycol, or polyesters having free hydroxyl g gzfi mgfggmfgigfiz groups, with a di-isocyanate in the presence of some l, lf twater and a catalyst. As the polymer forms in thisreacdimethyldodecylphosphinu oxide tion, the water reacts withisocyanate groups partly to cause cross-linking and partly to cause theformation of ethyleneimine is quaternized prior to being added, to

amine groups, at the same time producing carbon diox-' ide which causesfoaming. In other cases trifluoromethane or a similar volatile materialcan be used as the blowing agent, or additional blowing agents. Thepolyurethane-polyalkyleneimine substrates herein are formed by theaddition of a polyalkyleneimine of the type noted above during theurethane polymerization process. The polyalkyleneimine is therebyincorporated in the polymer by covalent bonds. Preferably thepolyurethane used herein is one made from a polypropylene glycol andeither toluene or naphthalene diisocyanate. The polyurethane canalternatively be derived from other di-isocyanates with other alkyleneoxides or with polyesters having free hydroxyl groups.

Procedures for preparing polyurethanepolyalkyleneimine copolymers aregiven below.

FOAM l Polyurethane foam containing about 3 percent by weightpolyethyleneimine is prepared as follows: 100 parts polypropylene glycol(avg. mol. wt. 2000), 50 parts toluene di-isocyanate, 5 partspolyethyleneimine (avg. mol. wt. 2000), 5 parts fluorotrichloromethaneand 0.l part stannous octanoate are intimately mixed and allowed toreact at about 50C 70C for about two hours. The resulting foam mass isthen cured by bringing the mass to a temperature of about 90C 100C fortwo minutes. The foam is then washed thoroughly with agitation to removeany excess polyethyleneimine and air dried. The resultingpolyurethanepolyethyleneimine copolymeric foam is suitable for use inthe articles and processes of this invention without further treatment.

In the above procedure, the polyethyleneimine is replaced by anequivalent amount of 50 percent SPEI and copolymers of polyurethane 50percent SPEI suitable for use herein are secured.

FOAM 2 A polyurethane foam containing about 3 percent by weight ofpolyethyleneimine wherein 25 percent of the nitrogen atoms arequaternized with methyl groups is prepared as follows: 100 partspolypropyleneglycol (avg. mol. wt. 2,000), 50 parts toluenedi-isocyanate, 5 parts polyethyleneimine (avg. mol. wt. 2,000), 5 partsfluorotrichloromethane and 0.1 stannous octanoate are intimately mixedand allowed to react at about 50C for about 2 hours. The resulting foammass is then treated with 2 parts dimethylsulfate at 70C for a period oftwo hours. Following this treatment, the resulting foam mass is cured bybringing the mass to a temperature of about IC for 2 minutes. The foamis then washed thoroughly with agitation to remove any excesspolyethyleneimine and dimethylsulfate; the mass is air dryed. Theresulting polyurethane-25 percent methyl quaternized polyethyleneiminecopolymeric foam is suitable for use in the articles and processes ofthis invention without further treatment.

In the above procedure, the dimethylsulfate is replaced by an equivalentamount of decyl iodide and s s a zsdiqy q m s ans-tfi Percent decylpolyethyleneimine suitable for use herein are secured.

In anwttift a tm t hsabs s ptos d rat p ythe polyurethane pre-polymermix. This is accomplished as follows: parts polyethyleneimine areadmixed with 50 parts ethyl iodide at 25C for one hour. The resultingproduct is the polyethyleneimine in which approximately 30 percent ofthe total nitrogen atoms are quaternized with ethyl substituents; thecounterion is iodide. The resulting quaternized polyethyleneimine isused to replace the polyethyleneimine in the procedure described in Foaml and a polyurethane foam containing the quaternized polyethyleneimineis secured.

In the foregoing procedure, the polyethyleneimine is replaced by anequivalent amount of polybutyleneimine and polypropyleneimine,respectively, and equivalent compositions containing the respectivequaternized polyalkyleneimine-polyurethane foams are secured.

EXAMPLE I Foamed polyurethane-polyalkyleneimine copolymer prepared inthe manner of Foam 1, above, is fashioned into cloths (about 8 inchessquare) weighing about 2 g., folded into bag-like containers, filledwith about 2 oz. of detergent composition A, above, and sealed, therebyproviding a laundering aid. Upon addition of the laundering aid to anaqueous laundry bath, the detergent composition dissolves from thetrapper cloth container and is released into said bath. Dirt and anionicdyes released from fabrics laundered in the bath are trapped in thesurface of the trapper cloth bag, which is then discarded.

The trapper cloth bag is prepared containing about 2 oz. of detergentcompositions B, C, D, E, H, I, J, K and L, above, respectively, in placeof detergent composition A, and equivalent laundering and dye and dirttrapping results are obtained.

In a modification of the above article a 4 in. X 4 in. X 1 in. Foam Isponge is soaked in detergent composition F and detergent composition G,above, respectively, and provides a laundering aid comprising a trappersponge impregnated with a detergent composition. Alternatively, thesponge is soaked in 20 percent (wt.) aqueous solutions of detergentcompositions A, B, C, D, E, H, I, J, K, and L, respectively, and dried,and trapper sponges impregnated with these detergent compositions aresecured. Said trapper sponges impregnated with detergents are added toaqueous laundry baths 50 and release therein the respective detergentcompositions while trapping dirt and anionic dyes. The polyurethane Foaml is replaced by an equivalent amount of the methyl quaternizedpolyethyleneimine Foam 2, described above, and equivalent results aresecured.

In a modification of the above articles, detergent formulations A, B, C,D, F, H, I, J, K and L, above, are each modified by adding a lipase, anamylase and a protease, respectively, in about 0.05 percentconcentration of said enzymes based on weight of detergent. Equivalentresults are obtained in that the fabrics are cleansed while the trapperadsorbs dirt and anionic dyes released into the laundry bath.

EXAMPLE n A aqztq r n aid somprisins a apasrplqth in d;-

tergent tablet is prepared as follows. A polyurethane prepolymer mix isformed from 100 parts polypropylene glycol (avg. mol. wt. 2,500), 25parts toluene diisocyanate, 25 parts naphthalene di-isocyanate, and 0.05parts stannous octanoate. The pre-polymer mix is extruded through a bathof polyethyleneimine and the resulting filaments cured at 90C-100C for 3minutes. The resulting filaments, which contain about 5 percent byweight of the polyethyleneimine copolymerized with the polyurethane, arewoven into trapper cloths.

A laundering aid comprising a trapper cloth prepared in the foregoingmanner in a detergent table is prepared as follows: the trapper cloth(about 6 in. X 6 in. X 1/16 in. weighing about 5 g.) is compacted byfolding into an object having the dimensions approximately 0.5 in. X 1in. X 2 in. About 2.5 oz. of detergent formulation A, above, is moldedaround the folded trapper cloth and compacted in an automatic press to atablet, said tablet containing in its interior said trapper cloth. Thedetergent tablet containing said trapper cloth is added to an aqueouslaundry bath at a temperature of about 1 10F; the detergent compositiondissolves and releases the trapper cloth which scavenges dirt andanionic dyes and substantially decreases dye transfer between thefabrics being laundered. In a modification of this laundering aid,detergent compositions B, C, D, E, H, l, J, K and L, above,respectively, are used to form said tableted detergent object containingthe trapper.

In the above compositions, the polyethyleneimine is replaced by anequivalent amount of polybutyleneimine and by 25 percent stearylatedpolyethyleneimine in which percent of the total nitrogen atoms arequaternized with methyl bromide and equivalent results are secured.

The above laundering aids comprising detergent compositions and trappersare prepared using the following trapper materials, all prepared byforming poly urethane from toluene di-isocyanate and a propyleneglycolin the presence of polyalkyleneimines and alkylated and alkanoylatedpolyalkyleneimines and quaternized polyalkyleneimines: polyurethane towhich is chemically affixed about 10% by weight of the followingpolyalkyleneimines, respectively: 50 percent stearoylateddi-ethyleneimine, 70 percent methylated triethyleneimine, 10 percentstearoylated dipropyleneimine, 50 percent methylated dibutyleneimine, 15percent stearoylated polypropyleneimine (avg. mol. wt. 20,000), percentdiethylated polymethyleneimine hydroxide (quaternarized; mol. wt.100,000), 10 percent methylated polybutyleneimine (avg. mol. wt. 2,000),15 percent hexanoylated polymethyleneimine (avg. mol. wt. 25,000), 50percent docosanoylated-50 percent ethylated polybutyleneimine (avg. mol.wt. 50,000), 5 percent octanoylated-5 percent methanoylatedpolymethyleneimine (avg. mol. wt. 10,000), 20 percent dihexylatedpolyethyleneimine fluoride (quaternarized; mol. wt. 3,000), 5 percentdocosylated polyethyleneimine (avg. mol. wt. 1,000), 100 percentdocosylated polybutyleneimine (avg. mol. wt. 100,000). In each instance,the released trapper cloth scavenges dirt and anionic dyes from aqueouslaundry baths and substantially inhibits dye transfer.

It is to be understood that the laundering aids of the present inventionare suitable for use inall manner of aqueous laundering processes. It iswell-known that such laundering processes can involve additional stepssuch as bleaching with hypohalite solutions and fabric softening andantistatic treatments involving quater nary ammonium salts. Suchlaundering, bleaching and treating processes are commonly carried outover a pH range of from about 3 to about 14. Such considerations areimmaterial to the practice of this invention in that the laundering aidsperform their cleaning and trapping function under all such conditionsand in the presence of any of these common laundry additives.

Furthermore, it is recognized that the quantity of trapper required toremove substantially all the dirt and dye from an aqueous laundry bathwill vary with the amount of dirt and dye released from the launderedcloths. Assuming a moderate-to-heavy dirt load and dye release, about a2 02. mass of the foamed trapper will remove substantially all dirt anddye released from one 6 pound laundry bundle washed in about 8 gallonsof water. More or less trapper can be employed, as desired.

What is claimed is:

l. A laundering aid consisting essentially of 1 a water-insolublesubstrate consisting of polyurethane chemically combined with from about0.1 percent to about 10 percent by weight of said substrate of apolyalkyleneimine material containing the moiety wherein y is an integerof from 1 to 4, z is an integer greater than 1, R is selected from thegroup consisting of hydrogen and alkyl and alkanoyl substituentscontaining from about 1 to about 22 carbon atoms, R is an alkyl groupcontaining from 1 to about 22 carbon atoms and X is an anion; and (2) awater-soluble detergent composition in releasable combination with saidsubstrate in an amount sufficient to provide good fabric cleansing.

2. A laundering aid according to claim 1 wherein the water-insolublesubstrate consists of polyurethane chemically combined with from about 1percent to about 10 percent by weight of polyethyleneimine.

3. A laundering aid according to claim 1 wherein the detergentcomposition comprises from about 10 percent to about percent by weightof a water-soluble organic detergent compound and from about 10 percentto about 90 percent by weight of a water-soluble detergency builder.

4. A laundering aid according to claim 3 wherein the organic detergentcompound is a member selected from the group consisting of alkali metalsoaps and water-soluble organic sulfonic acid reaction products havingin their molecular structure an alkyl substituent containing from about8 to about 22 carbon atoms and a sulfuric acid or sulfonic estersubstituent and wherein the detergency builder is a member selected fromthe group consisting of sodium nitrilotriacetate, potassiumnitrilotriacetate, sodium mellitate, potassium mellitate, sodiumcitrate, potassium citrate, sodium carbonate, potassium carbonate,sodium silicate, potassium silicate, sodium oxydisuccinate, potassiumoxydisuccinate, sodium phloroglucinoltrisulfonate, potassiumphloroglucinoltrisulfonate, sodium (ethylenedioxy)diacetate andpotassium (ethylenedioxy)diacetate.

5. A laundering aid according to claim 1 wherein the substrate is in bagconformation releasably containing the detergent composition.

6. A laundering aid according to claim 1 wherein the detergentcomposition is in tablet form and the substrate is incorporated in saidtablet.

7. A laundering aid according to claim 1 wherein the substrate is insponge form releasably containing the detergent composition.

8. A process for trapping dirt and anionic dyes in laundering bathscomprising adding to said bath a detergent composition in an amountsumcient to provide good fabric cleansing and a water-insolublesubstrate consisting of polyurethane chemically combined with from about0.1 percent to about percent by weight of said substrate of apolyalkyleneimine material containing the moiety

2. A laundering aid according to claim 1 wherein the water-insolublesubstrate consists of polyurethane chemically combined with from about 1percent to about 10 percent by weight of polyethyleneimine.
 3. Alaundering aid according to claim 1 wherein the detergent compositioncomprises from about 10 percent to about 90 percent by weight of awater-soluble organic detergent compound and from about 10 percent toabout 90 percent by weight of a water-soluble detergency builder.
 4. Alaundering aid according to claim 3 wherein the organic detergentcompound is a member selected from the group consisting of alkali metalsoaps and water-soluble organic sulfonic acid reaction products havingin their molecular structure an alkyl substituent containing from about8 to about 22 carbon atoms and a sulfuric acid or sulfonic estersubstituent and wherein the detergency builder is a member selected fromthe group consisting of sodium nitrilotriacetate, potassiumnitrilotriacetate, sodium mellitate, potassium mellitate, sodiumcitrate, potassium citrate, sodium carbonate, potassium carbonate,sodium silicate, potassium silicate, sodium oxydisuccinate, potassiumoxydisuccinate, sodium phloroglucinoltrisulfonate, potassiumphloroglucinoltrisulfonate, sodium (ethylenedioxy)diacetate andpotassium (ethylenedioxy)diacetate.
 5. A laundering aid according toclaim 1 wherein the substrate is in bag conformation releasablycontaining the detergent composition.
 6. A laundering aid according toclaim 1 wherein the detergent composition is in tablet form and thesubstrate is incorporated in said tablet.
 7. A laundering aid accordingto claim 1 wherein the substrate is in sponge form releasably containingthe detergent composition.
 8. A process for trapping dirt and anionicdyes in laundering baths comprising adding to said bath a detergentcomposition in an amount sufficient to provide good fabric cleansing anda water-insoluble substrate consisting of polyurethane chemicallycombined with from about 0.1 percent to about 10 percent by weight ofsaid substrate of a polyalkyleneimine material containing the moiety 9.A process according to claim 8 wherein the water-insoluble substrateconsists of polyurethane chemically combined with from about 1 percentto about 10 percent by weight of polyethyleneimine.